EP0192528B1 - Procédé de fabrication d'hydrogeno-silanes - Google Patents

Procédé de fabrication d'hydrogeno-silanes Download PDF

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Publication number
EP0192528B1
EP0192528B1 EP86400175A EP86400175A EP0192528B1 EP 0192528 B1 EP0192528 B1 EP 0192528B1 EP 86400175 A EP86400175 A EP 86400175A EP 86400175 A EP86400175 A EP 86400175A EP 0192528 B1 EP0192528 B1 EP 0192528B1
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EP
European Patent Office
Prior art keywords
formula
tris
amine
equal
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86400175A
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German (de)
English (en)
French (fr)
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EP0192528A1 (fr
Inventor
Gérard Soula
Jean-Luc Lepage
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
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Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0192528A1 publication Critical patent/EP0192528A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/04—Hydrides of silicon
    • C01B33/043—Monosilane

Definitions

  • the present invention relates to a process for the production of hydrogen silanes; it relates more particularly to the manufacture of monosilane.
  • European Patent No. 86,191 also describes a process for the reduction of compound MX with a sodium hydride, the reducing agent used being a sodium hydroborate.
  • Such compounds are already used in combination with an ionic mineral salt to catalyze the disproportionation and distribution reactions of haloalkalisanes, as described in European Patent No. 138,669.
  • halosilanes which are used according to the process of the invention are those which have the formula R n H m SiX 4 ( n + m) in which n can have the values 0, 1, 2 or 3 and m the values 1, 2 or 3 and R, when it exists, is chosen from alkyl or aryl and / or alkoxy radicals and preferably the radicals: methyl, ethyl, propyl, isopropyl and / or phenyl, X is chosen from halogen and preferably represents chlorine and alkoxy groups and preferably represents methoxy or ethoxy groups.
  • silicon tetrachloride, trichlorosilane, dichlorosilane, dimethyldichlorosilane, methylhydrogenodichlorosilane, diphenyldichlorosilane, phenyltrichlorosilane, methylphenyl dichlorosilane or methylphenyl dichlorosilane are used.
  • the alkali or alkaline earth hydrides MHp used according to the invention are preferably chosen from: lithium hydride, sodium hydride, calcium hydride or magnesium hydride.
  • the catalyst is a sequestering agent of formula: N- [CHR 1 -CHR 2 -O- (CHR 3 -CHR 4 -O) n -R 5 ] 3 (I) in which n is an integer greater than or equal to 0 and less than or equal to 10 (0 ⁇ n ⁇ 10), R 1 R 2 , R 3 and R 4 identical or different represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms and R s represents an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical or a radical -CmH2m-0 or C m H 2m + 1 -0-, where m is between 1 and 12 (1 ⁇ m ⁇ 12).
  • a sequestering agent of formula (I) is used in which Ri, R 2 , R 3 and R 4 represent a hydrogen atom or a methyl radical, Rs and n having the meaning former.
  • n is greater than or equal to 0 and less than or equal to 6 and for which Rs represents an alkyl radical having from 1 to 4 carbon atoms.
  • the amines used are known as such in the prior art.
  • the French patent 1,302,365 cites the production of tertiary amines N- (CH 2 -CH 2 -O-CH 3 ) 3 and N- (CH 2 -CH 2 -0-CH 2 -CH 2 -O-CH 3 ) 3 as by-products of the synthesis of the corresponding primary and secondary amines, these primary and secondary amines being products of interest as intermediates for the synthesis of pharmaceutical substances, as corrosion inhibitors, as intermediates for the synthesis of chemicals of interest in agriculture and as emulsifiers.
  • the sequestering agent can be grafted onto a crosslinked organic polymer, thus the present invention also relates to a process for the production of hydrogen silane by reduction of halosilane by an alkali hydride in a solvent.
  • a catalyst characterized in that the catalyst is a grafted sequestering agent constituted by a crosslinked organic polymer support and by a plurality of functional groups, fixed on said support, of general formula: in which Ri, R2, R 3 , R 5 , R 6 and R 7, which are identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, R ' 5 and R' 8, which are identical or different, represent a hydrogen atom, an alkyl or cycloalkyl radical having from 1 to 12 carbon atoms, a phenyl radical, a -C q , H 2 q ' -0 ⁇ - or C q' H 2q '+ 1 -0 ⁇ - radical with q 'greater than or equal to 1 and less than or equal to about 12, and in which n', m ', and p' identical or different are greater than or equal to 1 and less than or equal to 10.
  • a supported sequestering agent consisting of a crosslinked organic polymer support and by a plurality of functional groups attached to said support, of general formula (II) in which Ri, R2, R3, R 5 , R 6 and R 7 identical or different, represent a hydrogen atom or the methyl radical and R ' 5 and R 8 identical or different represent a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms.
  • n ', m' and p ', identical or different are greater than or equal to 1 and less than or equal to 6.
  • the support can be derived from any crosslinked organic polymer comprising groups which can be substituted by the functional groups of formula (II).
  • organic polymers suitable for the present invention mention may be made of polymers derived from vinylaromatic compounds such as styrene, methylstyrene and copolymers of vinylaromatic compounds and of C 4 -C 6 conjugated dienes such as copolymers of styrene and butadiene and styrene and isoprene.
  • polystyrene As the organic polymer, the crosslinking agent then being, according to a preferred embodiment, divinylbenzene.
  • the cross-linking rate is an important factor. It is indeed necessary that the functional groups of formula (II) grafted onto the polystyrene are active. For this, it is necessary that the molecules of the solvent in which the sequestering agent supported will be used, in the applications specified below, penetrate inside the polymer. For this purpose, it is necessary that the degree of crosslinking is not too great in order not to prevent the penetration of the solvent and of the reagents. It is preferred to use a polystyrene whose crosslinking rate by divinylbenzene is less than about 10%. Even more preferably, the crosslinking rate is less than approximately 5%.
  • the substitutable group is preferably chlorine or bromine of the chloro or bromo methyl radical - CH 2 CI or -CH 2 Br attached to the benzene nucleus of the polystyrene.
  • the percentage of benzene nuclei of the polystyrene carrying a functional group is greater than 5%. Even more preferably, this percentage is greater than 10%.
  • Preferred supported sequestering agents can be represented by the following formula: derived from chloro or methyl bromo polystyrene crosslinked by divinylbenzene of formula: where X represents Ci or Br.
  • the process according to the invention is generally carried out and preferably in the presence of a solvent, the sequestering agent being able to play the role of solvent itself.
  • This solvent must meet a certain number of conditions: it must be solubilizes the starting halosilane; it must also be chemically inert with respect to the silanes introduced or formed and the alkali or alkaline earth hydride used.
  • the minimum amount of solvent used is preferably such that the alkali or alkaline earth hydride is in suspension in the reaction medium.
  • a solvent is chosen such as, for example, chlorobenzene, orthodichlorobenzene, benzene, toluene, cyclohexane, heptane, dichloroethane, methylene chloride, tetrahydrofuran, dioxane, dimethoxyethane .
  • the process of the invention is carried out at a temperature between -30 ° C and the boiling temperature of the reaction medium, preferably between room temperature and the boiling temperature of the reaction mixture.
  • the hydrogen silane obtained can be separated as it is formed. It is possible to operate at a temperature close to ambient temperature, that is to say between 0 and 50 ° C., this constitutes one of the fundamental advantages of the process according to the invention.
  • the molar ratio between the sequestering compound and the alkali or alkaline earth hydride is between 5 and 0.0001 and preferably between 0.5 and 0.001.
  • the molar proportion between the hydride and the halosilane is generally close to stoichiometry. A slight excess of hydride may, however, be preferable to completely reduce the halosilane. This excess is preferably between 10 and 300 mol%.
  • the reduction reaction is preferably carried out by slowly introducing the halosilane into the reaction medium, moreover it may be advantageous to cool the reaction medium to avoid an excessive increase in temperature which would favor the secondary reactions of formation of by-products.
  • the hydrogen silanes obtained by the reduction reaction can be separated as they are formed.
  • the grafted sequestering compounds used according to the invention make it possible to work preferably continuously on a column, while the non-grafted sequestering compounds make it possible to work preferably discontinuously.
  • Sequestering agents of formula (I) used in the process according to the invention can be prepared as described in the French patent application published under No. 2,450,120.
  • the present invention thus makes it possible to effect the reduction of the halosilanes at room temperature and with exceptional productivity and using small amounts of catalyst.
  • the reaction medium is heated to 50 ° C. at the start of casting in order to initiate the reduction reaction of diphenyldichlorosilane. Once the reaction has started, the significant exotherm makes it possible to maintain the temperature of the medium at approximately 120 ° C. A slight heating is necessary at the end of casting to maintain this temperature.
  • the reaction medium is heated to 130-150 ° C for 1 hour after the pouring of (C 6 , H 5 ) 2 SiCl 2 .
  • Apparatus used 50 ml flask with magnetic stirring, surmounted by an ascending cooler and a dropping funnel.
  • Phenyltrichlorosilane is introduced, via the dropping funnel, into the flask containing TDA 1, the solvent and lithium hydride.
  • the reaction begins at the start of the casting, at room temperature; significant exotherm requires cooling the reactor in order to keep the temperature below 80 ° C.
  • the reaction medium is heated to 120 ° C.
  • reaction medium is then brought to 95 ° C. for 4 h.
  • the temperature of the reaction medium is up to 40 ° C.
  • the apparatus used in this example is as follows:
  • TDA 1 and lithium hydride are charged after inerting the argon apparatus (test carried out in the absence of solvent).
  • HSiCl 3 is introduced at constant flow rate via a positive displacement pump.
  • the reduction reaction which takes place even at 0 ° C is strongly exothermic.
  • the temperature of the reaction medium rises rapidly to 45 ° C., despite the vigorous cooling.
  • the reaction stops when the transformation rate of LiH reaches approximately 60%.
  • the low level of TDA 1 in the medium necessitates limiting the cooling to approximately 15 ° C. at the start of the reaction in order to initiate it, which does not start at 0 ° C.
  • the cryogenic fluid is again cooled to 0 ° C in order to limit the temperature in the reactor.
  • the flow rate of SiH 4 produced is 1.86 moles / h.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
EP86400175A 1985-02-04 1986-01-29 Procédé de fabrication d'hydrogeno-silanes Expired EP0192528B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8501486 1985-02-04
FR8501486A FR2576902B1 (fr) 1985-02-04 1985-02-04 Procede de fabrication d'hydrogeno-silanes

Publications (2)

Publication Number Publication Date
EP0192528A1 EP0192528A1 (fr) 1986-08-27
EP0192528B1 true EP0192528B1 (fr) 1989-05-24

Family

ID=9315891

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86400175A Expired EP0192528B1 (fr) 1985-02-04 1986-01-29 Procédé de fabrication d'hydrogeno-silanes

Country Status (6)

Country Link
US (1) US4629801A (en, 2012)
EP (1) EP0192528B1 (en, 2012)
JP (1) JPS61233692A (en, 2012)
CA (1) CA1258359A (en, 2012)
DE (1) DE3663521D1 (en, 2012)
FR (1) FR2576902B1 (en, 2012)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009056731A1 (de) 2009-12-04 2011-06-09 Rev Renewable Energy Ventures, Inc. Halogenierte Polysilane und Polygermane

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824657A (en) * 1985-11-27 1989-04-25 E. I. Du Pont De Nemours And Company Process for reducing silicon, germanium and tin halides
US4774347A (en) * 1988-02-29 1988-09-27 Dow Corning Corporation Removal of chlorinated hydrocarbons from alkylsilanes
US4927616A (en) * 1989-10-02 1990-05-22 Ethyl Corporation Preparation of silane and amine alanes
JP2551901B2 (ja) * 1991-07-26 1996-11-06 エフ エム シー コーポレーション 接触アルキル化方法
EP3684778B1 (en) * 2017-09-20 2023-08-02 Momentive Performance Materials Inc. Integrated process for the manufacture of methylchlorohydridomonosilanes
EP3853235A1 (en) * 2017-09-20 2021-07-28 Momentive Performance Materials Inc. Process for the production of organohydridochlorosilanes
CN120058769A (zh) * 2023-11-28 2025-05-30 江苏南大光电材料股份有限公司 提高芳香基氯硅烷还原制备芳香基硅烷转化率的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1473374A (fr) * 1965-03-03 1967-03-17 Ceskoslovenska Akademie Ved Procédé pour la réduction de combinaisons d'halogéno-silicium
US4295986A (en) * 1979-05-14 1981-10-20 Gordon Roy G Low temperature catalytic reduction
US4291167A (en) * 1980-07-28 1981-09-22 Nalco Chemical Company Preparation of tetramethyldisilane from 1,2-tetramethyldichlorodisilane
JPS57196716A (en) * 1981-05-29 1982-12-02 Mitsubishi Metal Corp Manufacture of monosilane
FR2552434B1 (fr) * 1983-09-28 1985-10-25 Rhone Poulenc Spec Chim Procede de fabrication de silane a partir de methyldichlorosilane et de chlorosilanes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009056731A1 (de) 2009-12-04 2011-06-09 Rev Renewable Energy Ventures, Inc. Halogenierte Polysilane und Polygermane

Also Published As

Publication number Publication date
EP0192528A1 (fr) 1986-08-27
FR2576902A1 (fr) 1986-08-08
JPS61233692A (ja) 1986-10-17
US4629801A (en) 1986-12-16
CA1258359A (fr) 1989-08-15
FR2576902B1 (fr) 1987-02-13
JPH0246597B2 (en, 2012) 1990-10-16
DE3663521D1 (en) 1989-06-29

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